Process of preventing deposits in internal combustion and jet engines employing additives



' tendencies. "fuel are primarily responsible for surface ignitionphenomena such as preignition and octane requirement increase (ORI)which is the tendency of spark ignition atet new

Patented July 25, 1961 PROCESS OF PREVENTING DEPOSITS IN INTER- NALCOMBUSTION AND JET ENGINES EM- PLOYING ADDITIVES Verner L. Stromberg,Webster Groves, Mo, assignor to Petrolite Corporation, Wilmington, DeL,a corporation of Delaware No Drawing. Filed Feb. 2, 1959, Ser. No.790,351 20 Claims. (Cl. 52.5)

This invention relates to deposit modifiers for substantiallyhydrocarbon fuels; More specifically, this invention relates tosubstantially hydrocarbon fuels containing deposit modifiers whichinhibit and/or prevent the deposit-forming tendency of hydrocarbon fuelsduring combustion, and/ or modify the deleterious effect of the formeddeposits, in both leaded and unleaded fuels, particularly in gasoline,jet fuels, etc., and to the process of inhibiting and/or preventing,and/or modifying the formation deposits in engines employing hydrocarbonfuels.

The smooth operation of an internal combustion engine depends upon thegradual propagation of the flame toward the cylinder walls and if thefuel-air mixture is ignited at many spots at the same time, progressivecombustion is interrupted. If several compressive Waves are created,they subject the unburned charge to unduly high pressure and temperatureso as to produce engine knock. This generally occurs if the cylinderdeposits, which contain carbonaceous materials and lead compounds,retain sufficient heat to ignite the fuel-air mixture before the flamewhich had been originated by the spark plugs reaches all parts of thecombustion chamber. Deposited lead compounds are believed to lower thetemperature at which the deposits glow and ignite the fuel and it isdesirable to reduce the deposits and/r neutralize the catalytic effectof such deposits in igniting the fuel. By so doing, these additiveslower the octane number required to prevent knock or surface ignition.

As automobile manufacturers annually raise the compression ratio oftheir automobile engines in the race for higher horsepower, the needbecomes greater for gasolines which burn cleanly, that is, have lowdeposit-forming Engine deposits which find their origin in the enginesin service to require higher octane fuels for proper performance. As aconsequence, gasoline manufacturers have placed increasing stress onreducing the depositforming tendencies of their fuels and have resortedto various additives either to reduce the amount of deposits or tominimize their effects.

The deposits formed in the combustion zone, particularly on the pistonhead and the exhaust valves, appear to have the most immediate effectsupon engine performance in that their presence requires a fuel having ahigher octane rating in order not to knock, thanis required by a new orclean engine. This means, in other words, that the octane value of afuel required by an engine containing deposits in the combustion zone inorder not to knock (referred to hereinafter as octane requirement) ishigher than the octane requirement of a clean engine. For example, aclean engine which requires a gasoline having an octane rating of 60 inorder not to knock is said to have an octane requirement of 60. If thesame engine, when dirty, i.e., with deposits in the combustion chamber,requires a gasoline having an octane rating of 75 in order not to knock,such as engine is said to have an octane requirement of 75, or an octanerequirement increase of 15. If a clean engine starts to get dirty, theoctane requirement rises with continued use. Finally there is no moreoctane requirement increase with continued use and apparently the enginehas then become as dirty as it is ever going to be with continued use,or if it becomes dirtier after a certain point, it does not require agasoline of greater octane value in order not to knock.

It has been found, for example, that the weight of material depositedupon the top or head of the piston reaches a maximum in a singlecylinder engine after approximately 20 hours of operation and thatthereafter it decreases slightly, possibly due to a flaking action,until it levels off after about 40 hours of operation. It has also beenfound that the weight of the material deposited upon the exhaust valvesreaches a maximum in the same engine after about 30 hours of operationand thereafter it decreases slightly and levels off after about 40 hoursof operation. The fact that the weight of deposits in the combustionzone first reaches a maximum value and then levels oif to a somewhatlower value while the octane requirement levels off at the maximum valueis believed to disprove the formerly accepted theory that the octanerequirement of an engine is proportional to the weight of deposits inthe combustion chamber.

The undesirable eifects of the deposits in the combustion chamber arefurther aggravated when tetraethyl lead is contained in the fuel becausethese deposits then are no longer primarily carbonaceous but containappreciable quantities of lead. Accordingly, it has been found that thetotal weight of deposits formed in the combustion zone is appreciablygreater when using a leaded fuel than when using a non-leaded fuel. Theoctane requirement increase of an engine operating on leaded fuel,however, is not in proportion to the difference in deposit weights. Fromthis it is concluded that the octane requirement increase of an engineis determined not so much by the quantity of material deposited as byits presence and character.

It has also previously been found that the increase in octanerequirement resulting from the formation of engine deposits is notattributable to a decrease in the thermal conductivity of the surfacesenclosing the combu'stion zone.

Since it has been found that the octane requirement increase of anengine is not determined solely by the quantity of material deposited inthe combustion zone and that it is not due to a decrease in the thermalconductivity of the surfaces enclosing said zone, it is believed that itis due to a catalytic action wherein the deposits in the combustion zoneact as catalysts to accelerate the oxidation of petroleum hydrocarbons.suggested that the proper approach to the problem of reducing the octanedemand increase of an engine is that of adding to the fuel a substancehaving an anti-catalytic effect, or, in other words, the effect ofsuppressing or inhibiting the catalytic properties of the depositsformed, especially the troublesome lead-containing deposits. 7

The use of lead compounds in gasolines to increase the octane ratingsthereof is extremely widespread. There are, however, several ratherserious adverse effects which accompany the use of leaded gasolines. Oneof these effects, the deposition of various lead compounds within thecombustion chambers of the engines, has been at least partially remediedby the use of halohydrocarbon scavengers such as ethylene dibromide andrelated compounds, for example those disclosed in US. Patents 2,398,281,2,490,606, 2,479,900, 2,479,902, 2,479,901, 2,479,903, etc. Anotheradverse effect which has been attributed to the lead anti-knockcompounds is mis-firing due to spark plug fouling. This spark plugfouling is quite prevalent under conditions of high temperature engineoperation and, particularly in the case of aircraft engines is a veryserious type of trouble.

As stated above, in recent years there has been .a

It has, therefore, been localities.

marked trend in the automotive industry toward utilizing internalcombustion engines having high compression ratios in passenger cars andtrucks. It has been found that this increase in compression ratiosresults in increased engine efiiciency whereby the motoring public isprovided with both greater power availability and greater economy ofoperation. High compression engines almost uniformly require fuels ofhigh octane number for most elficient operation. Of the several methodsof raising the octane number of gasoline developed to date, that ofutilizing an anti-knock agent, particularly of the organolead type, hasbeen most successful. Although such anti-knock agents have been providedwith corrective agents commonly known as scavengers, which effectivelyreduce the amount of metallic deposits in the engine by forming volatilemetallic compounds which emanate from the engine in .the exhaust gasstream the accumulation of engine deposits in combustion chambers and onother engine parts such as pistons, valves, and the like cannot beentirely prevented. This accumulation of deposits .is particularlyprevalent when the vehicles are operated under conditions of low speedand high load as encountered in metropolitan As a result of the notableimprovements in fuel anti-knock quality, which have been-made in recentyears, such deposits present but a few minor problems in low compressionengines, whereas with engines of higher compression ratios, two moreserious problems are becoming increasingly prevalent, those ofdetonation can successfully be obviated by the utilization of organoleadanti-knock agents such as tetraethyllead, it has been found that theseverity of the wild ping problem often increases with the octanequality of the fuel. Hence, the automotive industry is faced with thedilemma resulting from the fact that each time the octane quality of thefuel is raised to coincide with increases in compression ratio,deposit-induced auto-ignition generally becomes more severe.

Ordinary detonation in the internal combustion engine has been definedas the spontaneous combustion of an appreciable portion of the charge,which results in an extremely rapid local pressure rise and produces asharp metallic knock. The control of ordinary detonation may be effectedby retarding ignition timing, by operating under part throttleconditions, by reducing the compression ratio of the engine, and byusing fuels having-high anti-knock qualities, that is, byusing anorganolead-containing fuel. Deposit-induced autoignition may be definedas the erratic ignition of the combustible charge by combustion chamberdeposits resulting in uncontrolled combustion and isolated bursts ofaudible and inaudible manifestations of combustion, somewhat similar toknocking. Aside from the nuisance experienced by the passenger caroperator, deposit-induced autoignition or wild ping often producesdeleterious effects inasmuch as it is a precurser of preignition.Therefore, wild ping results in rough engine operating conditions-andvery often increases the wear of engine parts, piston burning and thelike. In contrast to ordinary detonation, deposit-induced autoignitionor wild ping cannot be satisfactorily controlled by retarding ignitiontiming nor by operating under part throttle conditions. Inasmuch asautomotive engineers are desirous of utilizing in internal combustionengines the highest compression ratios permitted by the commerciallyavailable fuels, the reduction of compression ratios to eliminate thisproblem is not desirable nor feasible. Indeed, it is the consensus ofopinion among the designers of internal combustion engines that enginedevelopments have heretofore been greatly hindered by the limitationsimposed by deposit-induced autoignition. It is-evident, therefore, thatthe present requirement for fuel having high anti-knock qualities shallbe greatly surpassed by future requirements. Notwithstanding attempts toattain these qualities byalternative means, it is entirely probable thatthe most satisfactory method. for the attainment. of high. octane fuels.shall. continue tov be. the. use

of anti-knock agents, particularly of the organolead type. As a result,there is a paramount need existing for a new and improved method foraltering the physical and chemical characteristics of deposits and formodifying the combustion process such that the detrimental effects ofdepositinduced autoignition may be markedly suppressed or be eliminated.

I have now found that a particular class of compounds effectivelycontrols (by inhibiting and/ or preventing and/ or modifying) thedeposit-forming tendencies of substantially hydrocarbon fuels, forexample gasoline, jet fuels and the like, with resulting advantages. Thehydrocarbon fuels of this invention are characterized by lowdepositforming tendencies with the result that an engine operatedtherewith shows exceptionally clean intake system combustion space,valves, ring belt area, cleaner spark plugs, etc. The low deposit levelin the engine, spark plugs, etc., minimizes surface ignition in all itsmanifestations, for example preignition, knock, wild ping, spark plugfouling, etc. The low deposit level reduces the engines octanerequirement increase, and deposits on surfaces contacted by thelubricating oi1,'such as piston skirts and cylinder walls, are verymarkedly reduced.

In addition, these compounds have an anti-catalytic effect, or, in otherwords, have the effect of suppressing or inhibiting the catalyticproperties of the deposits found, especially the troublesomelead-containing deposits. Furthermore, these compounds are alsoeffective corrosion inhibitors.

The compositions of this invention are the reaction products of (l) ASA(alkenyl 'succinic anhydride) or its equivalents and (2) amines whichare capable of undergoing reaction with ASA. These products also includethe reaction products of ASA with amines containing other functionalgroups, for example, hydroxy groups. They also include amines which areincapable of reaction with ASA at the amino position but can be reactedat another position, for example at the hydroxy position, such as wouldoccur where a hydroxylated tertiary amine such as NE (CH CH OH) or wherea prior acyl-ated hydroxylated amine such as 0 CHZCHZOH RCN CHzCHzOH arereacted with ASA.

The reaction products advantageously contain some unreacted carboxylicgroups. These products can be characterized by the following formulawhere is residue of the amine, Zis O-, NH, NR, or N% wherein R is asubstitutedgroup, for example hydrocarbon group (methyl, ethyl, propyl,etc.), comprises an ASA residue and x and y are whole numbers. Sincemonoas well as polyamines can be employed, the amines which can bereacted with ASA include monoamines, polyamines, hydroxylmonoamines andhydroxylpolyarnines. Poly-amines include cyclic compounds containingmore than one nitrogen group such as the cyclic amidines, for exampleimid'azolines, tetrahydropyrimidines, etc.

Substantially any amine capable of reaction with ASA may be employedprovided the product forrned is sufficiently soluble in the fuel to beeffective as deposit modifiers.

In addition, the products formed, where they contain unreact-edcarboxylic groups, can be employed in the form of their salts.Satisfactory salts, can be prepared from the aminesdisclosed.hereinbyernploying an excessof the .amine reactant,particularlvaftenthe main reaction,

i.e. amidification, esterifioation, is complete. Thus, the product wouldbe wherein B is the basic material. Thus, B can be one of the basicamino constituents disclosed herein, for example, monoamine,hydroxylated monoamines, polyamines, hydroxylated polyamines, and othervariations disclosed herein. Some specific examples of basic materialsinclude butylamine, cyclohexylamine, toluidine, benzylamine, pyridine,and the like. However, the metals which form cations generally leave aresidue on combustion and are not generally employed, such as alkalimetals, alkali earths, etc. Thus, it should be understood thatthe claimsencompass the amine salts disclosed herein.

MONOAMINES Monoamines may be defined by the formulae RNH R NH, R N,where R is a hydrocarbon or a substituted hydrocarbon group, forexample, alkyl, cycloalkyl, aryl, alkenyl, substituted aryl, aheterocyclic radical, etc. Although the tertiary amine, R N, isobviously not capable of reaction with ASA to form an amide since it hasno reactive nitrogen group, it is capable of forming salts which may beeffective.

The monoamines most advantageously employed are those amines where R isas follows: octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl,octadecenyl, octadecadienyl, octadecatrienyl, mixtures of the foregoingradicals as derived from tallow, soybean, coconut oil and other animaland vegetable oils, and hydrocarbon radicals derived from the acids ofrosin and tall oil, such as abietic acid, dehydroabietic acid,dihydroabietic acid and tetrahydroabietic acid.

Provided the final product is soluble in the fuel, the R group or theamine can vary widely, for example from 1-30 or more carbons, butpreferably from 8-22 carbon atoms. Thus, when the ASA has suflicienthydrocarbon content to render the product soluble the R in the amine canbe a lower hydrocarbon radical for example methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, etc. In addition, isomers, unsaturated analogues,etc., can also be employed, for example, isopropyl amine, isobutylamine, secondary butyl amine, allyl amine, etc.

Examples of commercial primary amines which can be employed are thearmeens manufactured and sold by Armour & Company of Chicago, Illinois,under the trade names Armeen CD, Armeen S Armeen 8D, Armeen 10D, Armeen12D, Armeen 14D, Armeen 16D, and Armeen 18D. Armeen CD is a mixture ofprimary amines prepared from coconut oil, Armeen SD is a mixture ofprimary amines prepared from soybean oil, and the other Armeens aremixtures of primary amines containing predominantly the number of carbonatoms specified in the code number.

Examples of commercial secondary amines are Armeen 2C and Armeen 2HT asdescribed in a circular entitled Secondary Armeens by Armour & Company.

Additional commercial amines that can be employed are those sold underthe trademark Primene by Rohm & Haas, which are described in theirTechnical Bulletin SP-33, dated December 1951, and in their otherbulletins. These amines have the general structure where R has abranched chain of from about l2l carbon atoms.

Aromatic amines include aniline, substituted anilines, benzylamines,naphthylamine, etc.

preparation.

Amines where R is a heterocyclic group include furyl amine. In certaininstances the amine group may be part of the heterocyclic structure forexample morpholine, pipen'd-ine, etc.

The proportions of the reactants can vary widely, for example from molarratios of one mole of monoamine to one mole of ASA to 2 moles of amineto one mole of ASA. Where ratios outside this range are employed, thereis obviously an excess of reactant, based on stoichiometry except thatsalts may be formed. Preferably the molar ratio of amine to ASA is 1 to1.

Neither time nor temperature appear critical since the reaction of ASAwith the monoamine is quite easily effected. However, for reasonablerates a temperature of at least 75 C. is apparently required, forexample temperatures of 75-150, but preferably -140" C. It is desirablenot to run the reaction above 150 because of possible deterioration ofthe reaction and products as Well as possible side reactions. The timeof reaction does not appear critical; however, a reaction time of atleast about /2 hour, for example from /2 hour-5 hours, but preferably2-3 hours. Time and temperature are, however, interdependent, and alonger period of time is required at lower temperatures.

The products of the reaction can vary depending on the conditions ofreaction, the mole ratios of reactants, the moles of water removed, etc.The reaction of the monoamine with one mole of ASA proceeds quitereadily to yield R 0 0 R 1l l' l 0H However, when more extremedehydrating conditions are employed such as when an azeotroping agent isemployed, the reaction can proceed further by either cyclizing to forman imide or by reacting to form the diamide Some of all the aboveproducts may be present in the reaction mixture.

In general, the compositions of this invention are prepared by addingone mole to ASA to one mole of amine in about 200 ml. of solvent (Xyleneis used in the examples) heating to about l40150 C., holding it at thistemperature for about 15 minutes and then allowing the reaction mixtureto spontaneously cool to room temperature (about 2 hours). The reactionvessel employed is equipped with a mechanical stirrer, thermometer andreflux condenser.

Example 16 One mole of a commercial C alkenyl succinic acid anhydrideand one mole of Armeen 12D are placed in 200 ml. of xylene. When thereactants are stirred, an exotherm occurs. This reaction mixture is thenheated to C., held there for about 15 minutes and then allowed to coolto room temperature with stirring. The reaction product is an ambercolored liquid.

In view of the above description and the fact that the preparation ofother compositions of this invention are prepared in the same manner, itwould be unnecessary and burdensomely repetitious to repeat the detailsof each Therefore, the prepared compounds are:

summarized in Table I. In the examples the following amines areemployed:

( l) Armeen CD (8) 'Cyclohexy] amine HYDROXYLATED MONOAMINE Thehydroxylated monoamines employed in this invention are monoaminescontaining at least one hydroxy group, usually in the form of an alkanolgroup (ROII) and may contain as many of these groups as there areavailable positions in the molecule, particularly at the aminopositions. Thus, they may be R/ '-1 rRoH for example monoethanol amine,diethylethanol amine, dipropylethanol amine, dipropylpropanol amine;

for example diethanol amine, ethyldiethanol amine, propyldiethanolamine;

NEmoH for example triethanol amine, tripropanol amine, tributanol amine;and the like, where R is hydrogen or a hydrocarbon or a substitutedhydrocarbon group, for example alkenyl, alkyl, cycloalkyl, phenyl, andthe like and R is a hydrocarbon group, for example, (CH where x is awhole number, preferably 2-8, CH z,

| CH3 C2115 and other members of the homologous series.

In addition, the R groups may be joined so as to form a heterocyclicring, which nitrogen group contains a hydroxy group, for instance, inthe case of piperidine and derivatives, for example alkyl piperidine,etc.

Monoamines can be treated with alkylene oxide, for

example, ethylene oxide, propylene oxide, butylene oxide,

pszt lme ox d nd other aliph t xi a y as w l as aromatic oxide such asstyrene oxide and similar compounds to form hydroxylated amines havingrepetitious ether linkages. The hydroxylated amines may be described bythe formula wherein X, Y, and Z are either hydrogen, hydrocarbon groupsor (OR) H groups (Z is a whole number, for example ll0 or higher, butpreferably 1) where R is the hydrocarbon moiety derived from alkyleneoxide, provided that the compound has a group, whether amino oroxygen-containing, which is capable of reaction with ASA to form anamide and/or an ester group. In addition, where one reactive group iscontained in the resulting molecule, one or more of the terminal OHgroups in the molecule may be blocked by an ether or an ester linkagefor example, compounds of the type These monoamines contain at least onehydroxyl radical and may have two or three or even more. For example, ifa primary amine such as ethylamine, propylamine, butylamine or the likeis reacted with two moles of glycide to form a tertiary amine oneobtains a compound having four hydroxyl radicals. Similarly, if a moleof triethanol, tripropanol, or tributanol amine is reacted with threemoles of glycide, one obtains a monoamine having as many as six hydroxylradicals.

Thus, any of the primary and secondary amines described undermonoa-mines may be oxyalkylated to form secondary or tertiary amineswhich can be reacted with ASA. In addition, the hydroxyamine formed fromoxyalkylation may also be employed for example those having a carboncontent in the main chain of greater than two for example in N(ROH)where R has more than two carbons in the main chain, as exemplified bydi-npropanolamine, di-n-butanolamine, di-n-pentanolamine,mono-n-propanolamine, mono-n-butanolamine, ethyl din-butanolamine,hexyl-n-hexanolamine, etc.

The proportions of reactants can vary widely, depending on the number ofactive amino or hydroxy groups on the amine, for example, one mole ofamine to one mole of ASA to one mole of amine to six or more moles ofASA to those amines having, more than one functional group.

THE PREFERRED HYDROXYLAT ED MONOAMINE EMBODIMENT In its preferredembodiment this invention relates to the reaction product of two molesof an alkenyl succinic acid or an anhydride thereof and one mole of anamino alkanol or substituted aminoal-kanol having at least three carbonatoms; and to the process of preparing this product. More particularly,this phase of the invention relates to a composition of matter preparedfrom the above reactants having one ester group, one amide group and twocarboxylic acid groups per molecule (also referred to as anester-amide-aicid). Still more particularly, this invention relates to acompound having the formula:

In addition, one may employ some of the corresponding imido compoundeither alone or in combination with the diacid, wherein Z is an alkyleneor substituted alkylene radical having at least three carbon atoms, forexample from 3 to 12 or more carbon atoms, but preferably 3 to 8 carbonatoms; wherein one of the Rs or R"s on each succinic moiety is analkenyl radical having at least 2 carbons, for example 2 to 32 or morecarbons, but preferably 8 to 18 carbons and the other R or R on eachsuccinic moiety is hydrogen; and wherein Y is hydrogen or a hydrocarbongroup, for example an aliphatic group preferably lower alkyl.

The aminoalkanols employed in preparing the product of this phase of theinvention contain alkylene or sub stituted alkylene radicals having atleast three carbon atoms and both an amino and a hydroxyl radical. Thesecan be expressed by the formula:

H Y-1 IZ-H wherein Z is an alkylene radical having at least three carbonatoms, for example 3 to 12 or more, but preferably 3 to 8 carbons; and Yis hydrogen or a hydrocarbon galloup, for example an aliphatic group,preferably lower Thus, Z is an alkylene radical which can bestraightchained or branched chain, for example propylene, butylene,pentylene, hexylene, heptylene, octy-lene, nony-lene, decylene, etc.,and isomers thereof, for example-impropylene, isobutylene, isopentylene,isohexylcne, isoheptylene, isooctylene, isononylene, isodecylene, etc.The alkylene radical can be straight chained singly branched, forexample CHz-OH: doubly branched CH3 CH3 C )H H- or multi-branched CH3CH3 -CH2 H-HOHretc. In addition, the alkylene groups can be substitutedwith other groups, for example aromatic groups, for ex ample phenyl,tolyl, etc. In such instances the alkylene radical need not have threecarbon atomsbut may have only two, for example it may be ethylenewherein the ethylene radical also contains an aromatic group such as aphenyl group, etc. The amino or alcohol group can be attached to thecarbon atoms of the alkylene radical which are primary, secondary, ortertiary carbons. The carbons to which these radicals are attached neednot be of the same type. For example, in isopropanol amine,

the preferred aminoalkanol, the alcohol radical is .attached to asecondary carbon atom while the amino group is attached to a primarycarbon atom. Examples illustrating various positions of attachment ofthe functional groups are:

-amino-4-octanol, 1-amino-2-hexano1, 2-amino-3-hexanol,2-amino-2-methyl-3-hexanol,

l-amino-4-hexanol, Z-amino-l-hexanol, 3-amino-2-hexanol,l-amino-Z-heptanol, Z-amino-S-heptanol, 3-amino 4-heptanol,l-amino-Z-octanol, 2-amino-3-octanol, 2-amino 21methyl,j j A B-octanol,3-amino-4-octanol, I Z-amino-l-octanol, S-amino-Z-octanol, etc,

Although the above aminoalkanols are illustrated with aminoalkanolcontaining primary amino groups, it should be understood thatcorresponding compounds containing amidifiable secondary amino groupscan also be employed. I

Thus, aminoalkanols corresponding to those mentioned herein except thatthey contain N-aliphatic groups, such as N-alkyl groups, for examplemethyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, octadecyl,cycloaliphatic, etc., isomeric alkyl groups, etc, can be employed inthis invention. In addition, N alkenyl or N-alkinyl groups can also beemployed.

One convenient method of preparing these aminoalkanols is to reactammonia or a primary amine with an alkylene oxide on another hydrocarbonoxide having at least 3 carbon atoms, for example propylene oxide,butyleno oxide, octylene oxide, styrene oxide, etc. Other methods ofpreparing these aminoalkanols are so well known to the art that it isunnecessary to repeat them here.

In general, the alkenyl succinic acid anhydride is reacted With theaminoalkanol in a proportion of 2 moles of alkenyl succinic acidanhydride for each mole of aminoalkanol. Of course, more than 2 moles ofalkenyl succinic acid per mole of aminoalkanol can be employed, leavingan excess of alkenyl succinic anhydride in the reaction mixture.

For example, when two moles of an alkenyl succinic acid are reacted withone mole of an aminoalkanol or two moles of an alkenyl succinic acidanhydride are reacted with one mole of an aminoalkanol, a reactionproduct is produced, representing the complete chemical interaction ofthe reactants. However, when three moles of an alkenyl 'succinic acidanhydride reactant are reacted with the aminoalkanol, a product isproduced which comprises a physical mixture of the reaction product plusthe unreacted talkenyl succinic anhydride.

The reaction which takes place can be expressed by the followingequation, wherein the units have the meaning heretofore specified:

is also formed. In addition, one obtains an imido containing compound ofthe formula:

In general, the compositions of this invention are prepared by addingtwo moles of ASA and one mole of the aminoalkanol to about 200 ml. of asuitable solvent (xylene is used in the examples), heating to 150 C.,holding it at this temperature for 5-10 minutes and then allowing thereaction mixture to spontaneously cool to room temperature The reactionvessel employed is equipped With a mechanical stirrer thermometer and areflux condenser.

Example 233 Two moles of tetna-propenyl succinic anhydride (532 grams)is stirred with 200 m1. of Xylene and one mole of isopropanol amine INHiCHrGH-OH (75 grams) is then added. This mixture is then heated toreflux at 150 C., allowed to remain at this temperature for fiveminutes, and then allowed to cool spontaneously to room temperature. Theproduct is the ester-amide-acid product corresponding to the reactants.

In view of the above description and the fact that the preparation ofother compositions of this invention are prepared in the same manner, itwould be unnecessary and repetitious to repeat the details of eachpreparation. Therefore, the compounds are summarized in the followingTable II.

TABLE II n l i i i HOC(|JHC HO-N-ZO -(|3H('|JHCOH R R n R 2-4 do do H2-5 "do do H2 $3 -CH2-O-H CH2(|JH- 2-6 do do H 2-7 do do CH3 2-8 dO do H(CH:)3--

2-9 Octenyl Octenyl H CH (Straight (Straight Chain). Chain) CH -OH 2-10do do 0H3 2-11 "d0 d0 C2115 (EH3 CH 2-12 dodo i H -oHgcH:-

F CH 213 do do CH CHCH CH-?H- H CH 2-16 do do H (CH 2-17 Octenyl OctenylH CH (Branched). (Branched). 2-18 rin rln CH -CH:CH 2-19 do dO .'C2H52-2fl rin rin H H 2-21 do do OH! I -CHr-CH TABLE II-Gontinued :E'xainpI'One of Re One of Rs Y z ''CH1?H 2 22 do do H 27-23 do do CH3 2-24 do doH (CH2)a 2-25 Decenyl Decenyl H (Straight (Straight CH2 C I CH3 CH2-CHCzHi F 2-28 do do H 2-29 do do on;

CH2-CH- CHg(I1H 2-30 do do H 231 do do CH3 2-32 --do. do H (CH2)3 2-33Tetrapropenyl Tetrapropenyl H CH 2-34 do do CH3 1 2-35 do do CaH5 CHzCH-(llHs 2-36 do do H 2-37 do do CH3 -CH CH 238 do do H 'CHz'CH- 2-39 do doCH3 -CH CIH- -do do; H (CHz)3 2-41 Triisobutenyl. .Triisobutenyl. H CH3o do CH3 l dO d0 C2115 -CHz-CH n v (EH3 2-44 do do H 2-45 do do CH CIJHZ-CH2CH H 2-46 do do H 2-47 do do CH d'o. 10 H -(CH)2 Dodeceiiyl"Dodecenyl H (csltlgraight gsfiraight E 31H am 2-50 do do CH CH3 2-51 dodo; CzH5 CH2-CH $113 H ona ([3112 '-cHroH CHzCH 2-54 do. H 2-55 do'.--CH3 Although the above compounds are preferred wherein 2 moles of ASAare reacted with 1 mole of the aminoalkanol, other ratios may also beemployed, for example 1 to 2 moles or less of ASA to 1 mole ofaminoalkanol.

PRE-ACYLATED HYDROXYAMINE Where the hydroxyamine contains anarnidifiable nitrogen group, it may be pre-reacted with a fatty acid toform an amidohydroxy amine, for example, compounds of the formulae isderived from the carboxylic acidand R and R" are hydrocarbon groups,preferably alkyl having 2 to 18 carbon atoms but preferably 2-8 carbonatoms. Thereupon, this prior acylated hydroxyarnine can be reacted withASA. For purposes of illustration and to save repetition, I willillustrate this phase of the invention with acylated dialkanolamines. 7V w 7 An advantageous aspect of the prior acylated phase of the presentinvention provides for new compositions of matter obtained by reacting afatty acid preferably containing at least about five carbon atoms permolecule with a dialkanolamine, in a molar proportion of about 1:1,respectively, to produce an intermediate product, and then reacting analkenyl succinic' 'acid anhydride with the intermediate product, forexample, in .a molar proportion varying between about 1:1, respectively,and about 2:1 respectively.

In general, the dialkanolamine reactants utilizable herein are thosecompounds having the structural'for mula R-OH wherein R and R arealkylene radicals or hydrocarbonsubstituted alkylene radicals, havingfor example between about two and about seven or more carbon atoms perradical. These radicals can be similar or dissimilar radicals.Ordinarily, they will be the same in any given molecule. Since it ismore diflicult to csterify secondary and tertiary alcohol groups, it ispreferable that the alkylene radicals do not contain secondary ortertiary carbon atoms attached to the hydroxyl group, so as to formsecondary and tertiary alcohol groups, respectively. However, because oftheir greater commercial availability, it is preferred to usediethanolamine and hydrocarbon-substituted diethanolarnines. Thesecompounds have the structural formula, HN(CHRCHROH) wherein R is ahydrogen atom or a hydrocarbon radical, preferably an alkyl radical.Non-limiting examples of the dialkanolamine reactants arediethanolamine; dipropanolamine; di-iso-propanolamine;2,2'-iminodibutanol-1; 3,3- iminodibutanol-l; 4,4-i.minodibutanol-1;di-tert-butanolamine; 3,3-iminodipentanol-2; 6,6'-im-inodihexanol-1 and7,7-iminodiheptanol-1.

Any fatty acid, or its anhydride or acid halide, can be reacted with thedialkanolamine reactant to produce the intermediate products used inpreparing the reaction products of the present invention. Fatty acidscontaining substituent groups, such as halogen atoms, nitro groups,amino groups, etc., are also applicable herein. The fatty acid reactantscan be branched-chain or straightchain, and saturated or unsaturatedaliphatic monocarboxylic acids, and the acid halides and acid anhydridesthereof. Accordingly, when the term fatty acid is used herein, it mustbe clearly understood that the term embraces fatty acids, fatty acidanhydrides, and fatty acid halides, and derivatives thereof.Particularly preferred are the fatty acids having relatively long carbonchain lengths, such as a carbon chain length of between about 8 carbonatoms and about 30 carbon atoms. Non-limiting examples of the fatty acidreactant are valeric acid; a-bromoisovaleric acid; hexanoic acid;hexanoyl chloride; caproic acid .anhydride; sorbic acid; aminovalericacid; amino hexanoic acid; heptanoic acid; heptanoic acid anhydride;Z-ethylhexanoio acid; a-bromo-octanoic acid; decanoic acid; dodecanoicacid; undecylenic acid; tetradecanoic acid; myristoyl bromide;hexadecanoic acid; palrnitic acid; oleic acid, heptadecanoic acid;stearic acid; linoleic acid; phenyl-stearic acid; xylylstearic acid;adodecyltetradecanoic acid; arachidic acid; behenic acid; behenolicacid; erucic acid; erucic acid anhydride; erotic acid; selacholeic acid;heptacosanoic acid anhydride; montanic acid; melissic acid;ketotriacontic acid; naphthenic acids; and acids obtained from theoxidation of petroleum fractions.

The fatty acid reactant is reacted with the dialkanolamine reactant in amolar proportion of about 1:1. A molar excess of dialkanolaminereactant, as much as 25 mole percent or more, can be used advantageouslyto ensure complete reaction. After the reaction is complete, the excess,unreacted dialkanolamiue reactant will be removed by usual means, suchas by Water washing or by distillation. In any event, the net resultwill be an intermediate product produced by reacting the reactants in a1:1 molar proportion.

Without any intent of limiting the scope of the present invention, it ispostulated that the reaction between the fatty acid reactant and thedialkanolamine reactant re sults in the formation of a dialkanolamide ofthe fatty acid. Thus, the reaction between valeric acid and thediethanolamine could proceed, theoretrically, in accordance with thefollowing equation:

On the other hand, a secondary reaction could take place between thehydroxyl groups of the diethanolarnine to form morpholine, or reactionscould occur simultaneously between two molecules of the fatty acid andboth the amino hydrogen and a hydroxyl group of the dietbanolamine, asset forth in the following equation (2) CHzCHz OHnCH:

204E900 on+rtN oiuion)iolntoou +2Hz ornlon The reaction of Equation 3would produce some unreacted diethanolamine in the reaction mixture, butthis reaction probably does not occur to an appreciable extent. It willbe apparent, however, that, in view of the foregoing, any designationassigned to these intermediate products could include all of the aboveproducts.

Without any intent of limitingthe scope of the present invention, it ispostulated that the reaction products contemplated herein are esteramideproducts of the dialkanolarnine reactant having at least one freecarboxylic 1 7 acid group. For example, when the amide of diethanolamine is reacted with two moles of decenyl succinic acid anhydride thereaction product can contain any, or several, products, such as thoseset forth in the following structural formulae:

HO (3-0 (H) 0101119 (331140 0 C-CH:

C4H9C ON 0 11 0 0 C-CH2 HO 0 0-0 (H) C (311140 0 C CHQCHC O O CgH4 NO CC4119 H20 0 O O C 114 HO O O OH CioHiv 021140 0 C CHflCHC O 0 (31H;

C4H9GON 7 000411 031140000152 HgCCOOCgHA HO O C CH HG C O OH I 0101119(5101119 or isomers thereof. The reaction products probably containother substances.

In the interest of brevity, they may be defined by reciting thereactants and the number of moles of each which are used. For example,the reaction product produced by reacting one mole of valeric acid withone mole of diethanolamine to produce an intermediate product, which isthen reacted with two moles of decenyl succinic acid anhydride'may bedefined as valen'c acid-l-diethanolamine+decenyl succinic acid anhydride(1:1:2).

Non-limiting examples of the reaction products contemplated herein arethose produced by reacting the following combinations of reactants:valeric acid+diethanolamine+etheny1 succinic acid anhydride (1:1:2);la-bromoisovaleric acid+di-propanolamine+ethyl succinic acid (1:1:1,8);'hexanoic acid+di-iso-propanolamine-lpropenyl succinic acid anhydride(1:1:1); hexanoyl ch1o1ide+2,2-iminobutano1-l-I-sulfurized propenylsuccinic acid anhydride (1: 1:2); caproic acidanhyd1ide+3,3'-iminodibutanol-l+butenyl succinic acid (1:2:4); sorbicacid|4,4 iminodibutanol 1+l,2 dichloropentyl succinic acid anhydride(1:1:1.5); aminovaleric acid+di-tert-butanolamine-I-hexenyl succinicacid (1:1:2); amino-hexanoic acid+3,3-iminodipentanol-2+sulfurized3-methylpentenyl succinic acid anhydride (1:1:1.2); heptanoicacid+6,6'-iminodihexanol-l+2,3-dimethylbw tenyl succinic acid anhydride(1:1:2); heptanoic acid anhydride+7,7-i.minodi-heptano1-1+1,2-

dibromo-Z-ethylbutyl succinic acid (1:2:2); Z-ethylhexanoicacid+diethanolamine+hepteny1 succinic :acidanliydride (121:1.7);a-bromooctanoic acid+dipropanolamine+l,2-diiodooctyl succinic acid(1:1:1); decanoic acid+di-iso-propanolamine+octenyl succinic acidanhydride (1:1:2); dodecanoic -acid-|-2,2 imjnodibutanol 1+2methylhepteny-l succinic acid anhydride (1:1:1); undecylenic'acid+3,3'-iminodibutanol-1-[4-ethylhexenyl succinic acid (1:1:2);tetradecanoic acid+4,4-iminodibutanol-1+diisobuteny1succinicacidanhydiide (1:1:2);. Y

myristoyl bromide+'di-tert-butanolamine+ 2-propylhexenyl succinic acidanhydride (1:1:1);

hexadecanoic acid+3,3'-iminodipentanol-2+decenyl succinic acid(1:l:1.6);

palmitic acid+6,6'-iminohexanol-l+decenyl succinic acid anhydride(1:1:2);

oleic acid+7,7'-iminodiheptanol-l+undecenyl succinic acid anhydride(1:1:1.4);

heptadecanoic acid+diethanolamine+1,2-dichloroundecyl succinic acid(1:1:2);

stearic acid-dipropanolamine-l-dodecenyl succinic acid linoleieacid-I-di iso propanolamine-I-2-propylnonenyl succinic acid anhydride(1:1:1);

xylylstearic acid+2,2' iminodibutanol l+triisobutenyl succinic acidanhydride (1:1:2); a dodecyl tetradecanoic acid+3,3' iminodibutanol 1+hentriaconteny1 succinic acid anhydride (1: 1:1); arachidicacid+4,4-iminodibutanol-l+hexacosenyl succinic acid anhydride (1:1:2);

behenic acid+di-tert-butanolamine+hexacosenyl succinic acid (1:1:1.2);

behenolic acid+3,3'-iminodipentanol-2+1,2-diiodotetracosenyl succinicacid anhydride (1:1:2);

erucic acid+6,6'-iminodihexanol-1+2-octyldodecenyl succinic acidanhydride (1:1:1.4);

erucic acid anhydride+7,7'-iminodiheptanol-1(1:2:2.8);

cerotic acid+diethanolamine+eicosenyl succinic acid anhydride (1:1:2);

selacholeic acid+dipropanolamine+1,2-dibromo-2-methylpentadecenylsuccinic acid anhydride (1:1:1);

heptacosanoic acid anhydride+di-iso-propanolarnine+octadecyl succinicacid anhydride (1:2:4);

montanic acid+2,2+-iminodibutanol-l 1 1 1 melissicacid+di-tert-butanolamine-|-sulfurized octadecenyl succinic acidanhydride (1: l :2); and

ketotriacontic acid+7,7-iminodiheptanol-l-l-hexadecenyl succinic acidanhydride (1:1:2).

THE POLYAMINES: (a) HYDROXYLATED (b) NON-HYDROXYLATED A wide variety ofreactive polyamines can be employed, including aliphatic polyamines,clycloaliphatic polyamines, aromatic polyamines, heterocyclic polyaminesand polyamines containing one or more of the above groups. Thus, theterm polyaminesT includes compounds having one amino group on one kindof radical, for example, an aliphatic radical, and another amino groupon the heterocyclic radical as in the case of the following formulae:

cyclic, having a reactive amino group. It also includes polyamineshaving other elements besides carbon, hy-

drogen and nitrogen, for example, those also containing oxygen, etc. Thepreferred embodiments of the polyamines are the alkylene polyamines, thehydroxylated alkylene polyamines and the cyclic amidines, andN-alkylated derivatives thereof.

Polyamines are available commercially and can be prepared by well-knownmethods. It is well known that olefin dichlorides, particularly thosecontaining from 2 to 10 carbon atoms, can be reacted with ammonia oramines to give alkylene polyamines. If, instead of using ethylenedichloride, the corresponding propylene, bu;

tylene, amylene or higher molecular weight dichlorides are used, onethen obtains the comparable homologues. One can also use alpha-omegadialkyl ethers such as CICI-I OCH CI; ClC-H CH OCH CH Cl, and the like.Such polyamines can be alkylated in the manner commonly employed foralkylating monoamines. Such alkylation results in products which aresymmetrically or non-symmetrically alkylated. The symmetricallyalkylated polyarnines are most readily obtainable. For instance,alkylated products can be derived by reaction between alkyl chlorides,such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride,and the like and a polyamine having one or more primary amino groups.Such reaction results in the formation of hydrochloric acid, and hencethe resultant product is an amine hydrochloridei The conventional methodfor conversion into the base is to treat with dilute caustic solution.Alkylation is not limited to the introduction of an alkyl group, but asa matter of fact, the radical introduced can be characterized by acarbon atom chain interrupted at least once by an oxygen atom. In otherwords, alkylation is accomplished by compounds which are essentiallyalkyloxyalkyl chlorides, as,for example, the following:

CH OC H Cl C H OC H Cl The reaction involving the alkylene dichloridesis not limited to ammonia, but also involves amines, such as ethylamine,propylamine, butylamine, octylarnine, decylamine, cetylamine,dodecylarnine, etc. Cycloaliphatic and aromatic amines are alsoreactive. Similarly, the reaction also involves the comparable secondaryamines, in which various alkyl radicals previously mentioned appeartwice and are types in which two dissimilar radicals appear, forinstance, amyl butylamine, hexyl octylamine, etc. Furthermore, compoundsderived by reactions involving alkylene dichorides and a mixture ofammonia amines, or a mixture of two different amines are useful.However, one need not employ a polyarnine having an alkyl radical. Forinstance, any suitable polyalkylene polyarnine, such as an ethylenepolyamine, a propylene polyamine, etc., treated with ethylene oxide orsimilar oxyalkylating agent are useful. Furthermore,

various hydroxylated amines, such as monoethanolamine,

wherein z is an integer varying between about two and about six.

In naming the polyalkylenepolyamine reactants, the nitrogen atoms areconsidered to be attached to the terminal carbon atoms of the maincarbon atom chain indicated in each compound name. For example, di-(l-methylamylene) triamine has the structural formula:

In numbering the main carbon atom chain, the carbon atom attached to aterminal -NH radical is designated as the carbon atom in the l-position.Similar alkylene groups recur throughout the molecule. Nonlimitingexamples of the polyalkylenepolyamine reactants are diethylene'tn'amine;triethylenetetramine; tetraethylenepentamine; di-(methylethylene) triamine; hexapropyleneheptamine; tri(ethylethylene) tetramine;pental-methylpropylene) -hexamine; tetrabutylenepentamine;hexa-(1,1-dimethylethylene) heptamine; di-(l-methylbutylene) triamine;pentaamylenehexamine; tri-(l,2,2- trimethylethylene) tetramine; di-(l-methylamylene) triamine; tetra-(l,S-dimethylpropylene)pentamine;pental,5-dimethylamylene-3-hexamine; di-( 1-methyl-4-ethylbutylene)-triamine; penta-( LZ dimethyll-isopropylethylene)hexamine;tetraoctylenepentamine; rtri-(l,4-diethylbutylene)tetramine;tridecylene-tetramine; tetra-(1,4-dipropylbutylene) pentamine;didodecylenetriarnine; tetratetradecylenepentamine;penta-(1-methyl-4nonybutylene) hexamine; tri-( 1,15-dimethylepentadecylene) -tetramine; trioctadecylenetetrarnine;dieicosylenetramine; di-(l,2-dimethyll4-nonyltetradecylene) triamine;di-( 1,l8-dioctyloctadecylene) triamine;penta-(l-methyl-Z-benzylethylene)hexamine;tetra-(l-methyl-3-benzyl-propylene) pentamine;tri-(l-methyl-1-phenyl-3-propylpropylene) tetramine; and tetra-(l-ethyl-2-benzylethylene)pentamine.

The polyamine can be alkylated with any alkyl halide which contains atleast one carbon atom and up to about thirty carbon atoms or more permolecule. It is especially preferred to use alkyl halides having betweenabout eight and about eighteen carbon atoms per molecule. Those havingbetween about 14 and about 18 carbon atoms are more particularlypreferred for certain products. The halogen portion of the alkyl halidereactant molecule can be any halogen atom, i.e., chlorine, bromine,fluorine, and iodine. In practice, the alkyl bromides and chlo rides areused, due to their greater commercial availability. Some non-limitingexamples of the alkyl halide reactant are n-but-yl bromide; n-butylchloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamylchloride; 'n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide;7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide;hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosylchloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride, andtr'iacontyl chloride.

The alkyl halides can be chemically pure compounds or of commercialpurity. Mixture of alkyl halides, having carbon chain lengths fallingwithin the range specified hereinbefore, can also be used. Examples-ofsuch mixtures are mono-chlorinated Wax and mono-chlorinated kerosene.Complete instructions for the preparation 'of mono-chlorowax have beenset forth'in United States Patent 2,238,790.

- The number of moles of alkyl halide reactant which is reacted witheach mole of polyalkylene polyamine reactant varies between about onemole and about (xl) moles, wherein x is the number of nitrogen atoms inthe polyalkylene-polyamine reactant molecule. In order to obtain anintermediate product-which can be used to produce the reaction productsof this invention, it is essential that at least one nitrogen atom inthe polyalkylenepolyamine reactant be left unsubstituted. Accordingly,the; maximum number ofmoles of alkyl halide reactant which is reactedwith each mole ofpolyalkylene-polyamine reactant will be one lessthanthe number of nitrogen atoms in the polyalkylene-polyamine molecule. Inaccordance with the present invention, a fewer number of moles ofalkylhalide reactant can be used. For example, if tetraethylenepentamineis utilized as the polyalkylenepentamine reactant, one, two, three, oreven four moles of an alkyl halide reactant can be reacted with eachmole thereof to produce intermediate products suitable for thepurposescontemplated herein. When five moles of alkyl halide reactant are used,the intermediate product is not utilizable in the production of thereaction products of the present invention.

As to the introduction of a hydroxylated group, one can use any one of anumber of well-knownprocedu'res such as alkylation, involvinga-chlorohydrin, such as ethylene chlorohydrin; glycerol chloroh'ydrin,or the like.

Such reactions are entirely comparable to the alkylation reactioninvolving alkyl chlorides previously described. Other reactions involvethe use of an alkylene oxide, such as ethylene oxide, propylene oxide,butylene oxide, octylene oxide, styrene oxide or the like. Glycide isadvantageously employed. The type-of reaction just referred to is Wellknown and results in the introduction of a hydroxylated orpolyhydroxylated radical in an amino hydrogen position. It is alsopossible to introduce a hydroxylated oxyhydrocarbon atom; for instance,instead of using the chlorohydrin corresponding to ethylene glycol, oneemploys the chlorohydrin corresponding to diethylene glycol. Similarly,instead of using the chlorohydrin corresponding to glycerol, one employsthe chlorohydrin corresponding to diglycerol.

From the above description it can be seen that man of the above alkylenepolyamines can be characterized by the general formula:

where the Rs, which are the same or diiferent, comprise hydrogen, alkyl,eycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylatedalkyloxyalkyl, etc., radicals, x is zero or a whole number of at leastone, for example 1 to 10, but preferably 1 to 3, and n is a wholenumber, 2 or. greater, for exampleZ-lO, but preferably 2-5. Of course,it should be realized that the amino or hydroxyl group may be modifiedby acylation to form amides, esters or mixtures thereof, prior toreaction with ASA provided the resulting compound contains a residualgroup capable of reaction with ASA, which group can be hydroxyl and/ oramino.

Cyclic aliphatic polyamines having at least one secondary amino groupsuch as piperazine, etc., can also be employed.

It should be understood that diamines containing a reactive amino groupmay be employed. Thus, where x in the linear polyalkylene amine is equalto zero, at least one of the Rs would have to be hydrogen, for example,a compound of the following formula:

Suitable polyamines also include polyamines wherein the alkylene groupor groups are interrupted by an oxygen radical, for example,

R x R or mixturesof these groups and alkylene groups, for ex- R x Rwhere R, n and x has the meaning previously stated for the linearpolyamine.

For convenience the aliphatic polyamines have been classified asnonhydroxylated and hydroxylated alkylene polyamino amines. Thefollowing are representative members of the non-hydroxylated series:

Diethylene triamine, Dipropylene triamine, Dibutylene triamine, etc.,

Triethylene tetram'ine, Tripropylene tetramine, Tributylene tetramine,etc.,

' Tetraethylene pentamine,

Tetrapropylene pentamine, Tetrabutylene pentamine, etc., Mixtures of theabove.

Mixed ethylene, propylene, and/or butylene, etc., polyamines and othermembers of the series.

The above polyamines modified with higher molecular weight aliphaticgroups, for example, those having from 8-30 or more carbon atoms, atypical example of which 1s where the aliphatic group is derived fromany suitable source, for example, from compounds of animal or vegetableorigin, such as coconut oil, tallow, tall oil, soya, etc., are veryuseful. In addition, the polyamine can contain other alkylene groups,fewer amino groups, additional higher aliphatic groups, etc., providedthe polyamine has at least one reactive secondary amino group.Compositions of this type are described in US. Patent 2,267,- 205.

Other useful aliphatic polyamines are those containing substitutedgroups on the chain, for example, aromatic groups, heterocyclic groups,etc., such as a compound of the formula where R is alkyl and Z is analkylene group containing phenyl groups on some of the alkyleneradicals.

In addition, the alkylene group substituted with a hydroxy group N CaaNca tN Examples of polyamines having hydroxylated groups include thefollowing:

'23 24 (HO C2114)nNGaH4NC2H4N(Ca 40 )a (!3Hz (l}Hg H N NH :115 (3:115\0/ NczHagcz t Hl l'R HO 01m wherein R is a hydrocarbon group,

(3113 CH; GH -0H2 H I NCaHgNCaHuN N NE HOCIHA 0 114011 I 0 Hz 0 Ha EN (0HQNH) 1H NCzH4NC2H4NC2H4N Where HO 01H; H H 02114015:2-undecylimidazoline Z-heptadecylimidazohne 0H3 C a 2-oleylimidazolineNCZHNCQHNCZHNCBHN l-N-decylaminoethyl, Z-ethylimidazoline H H H t tZ-methyl, 1-hexadecylaminoethylaminoethylimidazoline CZECH1-dodecylaminopropylimidazoline HO C2114 CZECHl-(stearoyloxyethyl)aminoethylimidazoline1-stearamidoethylaminoethylirmdazoline NQENWENQRNWEN2-heptadecyl,4-5-dimethylimidazoline CH3 0 31-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazolineThe preparation of cychc lmidazohnes and tetrahydro-ZhePtadecYLLmethYlaminoethYl tetrahydmpyrimidine Pyramides is W611 knownSee Patents 2,466,517, 4-methyl,2-dodecyl,l-methylaminoethylaminoethyltetra- 2,488,163, Re. 23,227. I hydropyrimidine Sultable cychc amldmesmdufle these shown In the It should also be realized in the preparationof the above Patents as well as the followmg cyclic amidine compoundsthat amides as well as cyclic N-CH: amidines maybe formed which cansubsequently be reacted with ASA. By controlling the reaction of thecarboxylic acids with polyamines so that one rather than 1?I'CH2 twomoles of water are removed, one obtains amides H rather than cyclicamides. If these amides possess'reactive group they can subsequently bereacted with ASA. Examples of amido-polyamines are shown in U.S. PatentR-O 2,598,213.

The following examples are presented for purposes of C H 40illustration. It must be strictly understood that this in- 2 4 2 ventionis not limited to the particular reactants and the molar ratios employedor in the operations and manipulations described therein. A wide varietyof other reactants and molar ratios, as set forth hereinbefore, may

NOH1 be used. JZHr-NH-C2HANHI Examples 3-6 N CH2 CHPN One mole ofan'alkylated polyamme (Duomeen T) H RC\ /0R RN-CHzCHzCHzNH;

N CHFI? (R is derived from tallow) is reacted with onemole of a f C ASAby heating the above reactants with an equal 11 amount of benzene at 130C. for about three hours.

The product is an amber liquid. %NOH2 In view ofthe above descriptionand thefact that the preparation of other compositions are prepared inthe same manner, it would be unnecessary and repetitious to repeat thedetails of each preparation. There, the com- 01H4 NH C1H4 NH C1H4 NH1pounds are summarized in the following table:

TABLE III Alkenyl ASA/poly- Example Group of Polyalmne amine, SA MolarRatio diethylene triamine 2:1 triethyleue tetramine 2:1 tetraethylenepentaminm 1:1 3-4 heptadecenyl dipropyleno triamiue 3:1

3-5 oetadecenyl... DuomeenS 1:1

Alkenyl A Al ly- Example Group of Polyamine amine, ASA Molar Ratio 3-6tetrapropenyL Duorneen '1 fi 1:1

RN CHQ3NH2 R derived from tallow.

3-7 octadeoenyl... OxyalkylatedgDuomeen S 1:1

RN(CH2)sNCz 4OH 3-8 heptadecenyL. Oxyalkylated Duomeen T 2:1

RN(CH2)5EC;1H4OH 3-9 tetrapropnyl- Amine 0LT (Monsanto) 2:1

12 2rCzH|NOnH4NH2 3-10 tetradeceny1 Oxyethylated Amine OLI 2:1

C12H25NC2H4NCH4NC2H4OH octenyl Dioetadecyl tetraethylene pentamine 3:1tetrapropeny1 dibutyl tetraethylenepentamine 2:1 do dioetyltetraethylenepentamine 3:1 octenyl trioctadecyl tetraethylenepenta 2:1 tetrapropenyloctadecyl diethylenetriamine- 1 1 -do dacyldiethylenetriamine 1:1 3-octadeeenyl--- Hydroxyethylethylenediamine 1:1

N-CH: 3 18 tetradeceny1 C11Haa0\ l 1:1 N H2 C2H4NH1 N--CH2 3-19. do012E250 2:1

OzH4NCzH4NCiu aa N-CH; a 3-20 do CaHnC CH2 1:1

CQHiNHfl N-CHz 3-21 do Ci1 asC i 1;1

N- Hg aHsN-CzHsOH 3-22 do Oleic acid prior acylated triethylenetetramine 1:1

(1:1 molar ratio). 3-23 heptadecenyL- Stearic acid prior acylatedtetraethylene penta- 1:1

mine (1:1 molar ratio).

| HOOC or an isomer thereof. The reaction products probably containother substances, such as cyclic imides of the formula The reactionproduct produced by reacting one mole of octyl bromide with one mole oftriethylenetetramine to produce an intermediate product which is thenreacted With two moles of decenyl succinic acid anhydride may be definedas the reaction product of octyl bromide(I)-triethy1ene-tetramine(I)-decenyl succinic acid anhydride(II).

Non-limiting examples of the reaction products contemplated herein arethose produced by reacting the following combinations of reactants:n-butyl bromide(II)-+ tetraethylenepentamine(I) +hexacosenyl succinicacid as hydrogen, sulfur, bromine, chlorine, or.iodine.' It is obvious,of course, that there must be at least two carbon atoms in the alkenylradical, but there is no real upper limit to the number of carbon atomstherein. However, it is preferred to use an alkenyl succinic acidanhydride reactant having between about 8 and about 18 carbon atoms peralkenyl radical. In order to produce the reaction products of thisinvention, however, an alkenyl succinic acid anhydride or thecorresponding acid must be used. Succinic acid anhydride and succinicacid are not-utilizable herein. For example, the reaction productproduced by reacting with succinic acid anhydride is unsatisfactory.Although their use is less desirable, the alkenylsuccinic acids alsoreact, in accordance with this invention; to produce satisfactoryreaction products. It has been found, however, that their usenecessitates the removal of water formed during the reaction and alsooften causes undesirable side reactions to occur to some extent.'Nevertheless, .the alkenyl succinic acid anhydrides and the alkenylsuccinic acids are interchangeable for the purposes of the presentinvention. Accordingly, when theterm alkenyl succinic acid anhydride, isused herein, it must be clearly understood that it embraces the alkenylsuccinic acids as well as their anhydrides, and the derivatives thereofin which the olefinic double bond has been saturated as set forthhereinbefore. Thus, it includes the hydrogenated alkenyl group, i.e.alkyl succinic acids and anhydrides. Non-limiting examples of thealkenyl'succinic acid anhydride reactant are ethenyl succinieacid'anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride;propenyl succinic acid anhydride; sulfurized propenyl succinic acidanhydride; butenyl succinic acid; Z-methyl-butenyl succinic acidanhydride; 1,2- dichloropentyl succinic acid anhydride; hexenyl succinicacid anhydride; hexyl succinic acid; sulfurized S-methylpentenylsuccinic acid anhydride; 2,3-dimethyl-butenyl succinic .:acid anhydride;3,3-dimethyl-butenyl succinic acid; 1,2-Ldibr'omo-2-ethylbntyl succinicacid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid;octenyl succinic acid anhydride; 2-methylheptenyl succinic acidanhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenylsuccinicacid anhydride; nonenyl succinic acid anhydride; f2propylhexenyl succinic acid anhydride; decenyl succinic acid; decenylsuccinic acid anhydride; '5-methyl- 2+isopropylhexenyl succinic acidanhydride; 1,2-dibromo- 2-ethyloctenyl succinic acid anhydride; decylsuccinic acid anhydride; undecenyl succinic acid anhydride;1,2-dichloro-undecyl succinic acid;- 3-ethyl-2-t-butylpentenyl succinicacid anhydride; dodecenyl succinic. acid .anhydride; dodecenyl succinicacid; 2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinicacid anhydride; tridecenyl succinic acid anhydride; tetradecenylsuccinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurizedoetadecenyl succinic acid; octadecyl succinic acid anhydride;1,2-dibromo 2 methylpentadecenyl succinic acid anhydride;8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acidanhydride; 1,2-dichloro-2- methylnonadecenyl succinic acid anhydride;2-octyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acidanhydride; hexacosenyl succinic acid; hexacosenyl succinic acid;hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acidanhydride.

The methods of preparing the alkenyl succinic acid anhydrides are wellknown to those familiar with the art. The most feasible method is by thereaction of an olefin with maleic acid anhydride. Since relatively pureolefins are diflicult to obtain, and when thus obtainable, are often tooexpensive for commercial use, alkenyl succinic acid anhydrides areusually prepared as mixtures by reacting mixtures of olefins with maleicacid anhydride. Such mixtures, as well as relatively pure anhydrides,are utilizable' herein. V

Thereaction between the alkenyl succinic acid anhydrideandthe aboveamines takes place at any temperature ranging from ambient temperaturesand upwards.

This reaction results in an amide and/or ester-formation reactioneffected by the well known reaction of the anhydride group with an aminoand an alcohol group. This reaction proceeds at any temperature, buttemperatures of above C. are preferred. Thus, the reaction can takeplace at 20 to 200 C., but preferably 100 to C.

The reaction between the alkenyl succinic acid anhydride reactant andamines proceeds smoothly in the absence of solvents. However, theoccurrence of undesirable side reactions is minimized when a solvent isemployed and therefore its use of a solvent is preferable. Since a smallamount of water might be formed when an alkenyl succinic acid anhydrideis used in the reaction, the solvent employed may be one which will forman azeotropic mixture with water.

The time of reaction is dependent on the size of the charge, thereaction temperature selected, and the means employed for removing anywater from the reaction mixture. Ordinarily, the addition of theanhydride reactant is substantially complete within a few minutes. Thesame products can be produced at temperatures below 100 C. for areaction time of less than one hour. In order to insure completereaction, particularly when the alkenyl succinic acid is employed, onemay continue heating for several hours. For example when benzene is usedas the solvent at a temperature of 100110 C., and water is removed, asoccurs with alkenyl succinic acid, heating may be continued for aboutfive hours. When water is formed during the reaction, as when an alkenylsuccinic acid is used, the completion of the reaction is indicated by asubstantial decrease in the formation of water. In general, the reactiontime will vary between several minutes and about ten hours.

Certain reaction products of this invention will be very viscous, oreven solid, rendering handling very diflicult from a commercialstandpoint. These difficulties can often be alleviated by producing thereaction products in a solutionor dispersion. The solvent can be addedto the reaction mixture of the aminoalkanol and alkenyl succinic acidanhydride reactant, before they are reacted with each other. In analternate procedure, the reaction product can be produced by the methodsmentioned hereinbefore, and then the solvent can be added to thereaction product while it is still hot. Dependent on the type ofreaction product involved and of final product desired, the solvent canbe used in any amount, thereby produc ing reaction products containingfrom about one percent by weight of solvent up to as much as 99 percentby weight of solvent.

All of the above compounds appear to be effective. However, for moreefl'ective action solubility in the fuel is highly desirable. To eifectsuch solubility there is an inter-relation between the number ofcarbons'on the alkenyl group and the number of carbons on the amine. Ingeneral, compoundscontaining a total of at least 10 carbons, for example10 to 50 carbons, but preferably 15 to 30 carbons can be employed,although those havirig lesser or more carbons can be employed undercertain circumstances. Taken in view of the above considerations, itcanbe seen that'the number of carbons of the amineand the alkenyl succinicacid can vary widely. However, in'practice I preferto employ an aminehaving at least one carbon, for example from one to fifty carbons, butpreferably three to' twenty-two carbons. In regard to the alkenyl.succinic anhydride the alkenylside chain should'have at leastthree'carbons, for example from three to twenty-four carbons, butpreferably four to eighteen carbons. 1

' In general, deposit-preventing, inhibiting and/or modifying amounts ofthe compounds are employed. For example, the products of this inventionareelfective as a deposit-control additives in concentrations between0.001 and 2.0 weight percent of the fuel. Generally, dirtier fuelshaving a higher concentration of olefinic components require higherconcentrations whereas cleaner burning premium fuels are improved withrespect to depositforming' characteristics by smaller concentrations. Ingeneral, dirtier gasolines require a concentration between 0.01 and 1.0percent whereas clean-burning premium fuels" only need a concentrationof between 0.001 and 0.5 percent. There is no critical upper limit froma functional viewpoint but economics dictate that the concentration beless than one percent.

The compounds in this invention are effective in controlling deposits inhydrocarbon fuels having boiling points up to about 500 F. or higher,although benefits also result when they are added to fuels containingresidual stocks of higher boiling point. The major application of theadditive is in gasoline for automotive engines wherein fuel-derivedengine deposits have become a particularly vexing problem. Thedeposit-forming properties of fuels designed for use in jets are asloimproved by the compounds of this invention. They find particularapplication in jet fuels which are used as cooling mediums prior totheir consumption. The compound-containing jet fuel is an excellent heatexchange medium since it is relatively free from deposits in the coolingsystem and burner nozzle where deposits cannot be tolerated.

The deposit-forming properties of both regular and premium gasolines,and aviation gasoline, whether leaded and of the non-leaded type areimproved by the addition of these compounds. The gasolines to which theyare added can be broadly defined as hydrocarbon fuels having a boilingpoint up to approximately 450 F.

Representaive compounds for the above classes are incorporated forexample in fuels used in automobile, aircraft, and jet engines.Laboratory tests are carried out employing these fuels in such systems.

EXAMPLES Test I Performance tests show that the present inventionproduces substantial improvement in engine cleanliness, as compared tothe same fuel not containing the additive. The test procedure involves a40 hour engine run on a dynamometer under conditions chosen tocorrelate, on an accelerated scale, with field performance. In this testa 216.5 cubic-inch, six-cylinder Chevrolet engine is run continuouslyfor forty hours as a speed of 1900 r.p.m. (plus or minus 25 r.p.m.)under an engine load of 36 BIL-P. (plus or minus 1 B.H.-P.). The jacketcoolant inlet temperature is kept at 155 F. minimum, the jacket coolantoutlet temperature is kept within two degrees of 170 F., and thecrankcase oil temperature is kept within two degrees of 190 F. Theair-fuel ratio is 14.5 (plus or minus 0.5) to 1. The spark advance is 35(plus or minus 3); The spark plug gap, ignition cam angle, valveclearance, exhaust back pressure and other similar conditions are alsomaintained at predetermined values. Before the test, the engine isdisassembled and cleaned, and a new set of piston rings is installed.The engine is given a standard two-hour break-in before the actual testis begun.

After the test run of 40 hours, the engine is dismantled and inspected,and is rated on ten items, as follows:

(1) Piston skirt varnish rating. (2) Cylinder wallvarnish rating.

'(3) Intake valve stem deposit rating.

(4) Intake valve tulip deposit rating.

(5 Intake port deposit rating.

(6) Overall engine sludge'rating; (7) Overall engine varnish rating.

On these first seven items, the rating runs between 0 for dirty to 10for clean.

a4 (l0) Tight ring rating (10 minus 0.5 demerit for each tight ring).

A perfectly clean engine will thus rate 100. A total rating of isconsidered acceptable if the piston skirt varnish is 7.5 or better.

The gasoline employed in the tests is composed of about 50% mixedthermal naphtha having about 95 400 F. boiling range, about 20% lightstraight-run naphtha having 95 250 F. boiling range, about 25% heavycracked (catalytic) naptha having 270-400 F. boiling range, and about 5%of light natural gasoline. It contains as additives about 1.75 ml. pergallon of tetraethyllead and an amine inhibitor in normal amounts. Itanalyzes 0.11% sulfur. Gum is present at about 2 to 5 mg. per 100 ml. inthe ASTM test and the copper dish test shows about 16-26 mg. of gum per100 ml. The gasoline has the following volatility specifications: 10%evaporated at 134150 'F., 50% at 244-250 F., and at about 360 F. Theapproximate composition of the gasoline is:

Percent Parafiins and naphthalenes, about 66 Olefins, about 16Aromatics, about 18 Sulfur, about 0:1 Phenols, about 0.4 Nitrogen, about0.001

The ASA-amine reaction products shown in the above tables when tested inconcentrations of 0001-05 Weight percent give cleaner engines andtherefore higher ratings than the control containing no additive.

An example of a high quality premium grade fuel with which similarresults are obtained comprises mainly fluid catalytically cracked stockand straight run gasoline. This fuel has a A.S.T.M. research octanerating, contains 2.74 ml. of TEL fluid per gallon, had an API gravity of60 to 65 and a boiling point range between and 400 F. the base fuel isnegative in the copper corrosion test and has an oxidation stability inthe A.S.T.M. test of 240 minutes minimum. This fuel also contains minoramounts of conventional gasoline inhibitors, namely, approximately 6pounds of N,N'-disecondary butyl-p-phenylenediamine, a gum inhibitor,per thousand barrels of gasoline, about 1.2 pounds ofN,N'-disalicylidene-1,2-diaminopropane, a metal deactivator, perthousand barrels of gasoline, and about 1.1 pounds of lecithin, atetraethyl lead stabilizer, per thousand barrels of gasoline.

Similar results are obtained with a high quality regular grade gasolinecomprising a mixture of thermal cracked stock, fluid catalyticallycracked stock and straight run gasoline. This regular base fuel has an87.0 A.S.T.M Research octane rating, contained 2.90 ml. of TEL pergallon, has an API gravity of 58.0 and a boiling range between 100 F.and 450 F.; the base fuel is negative in the copper corrosion test andhas an oxidation stability in the A.S.T.M. test of 530 minutes minimum.The reference fuel also contains minor amounts of gasoline inhibitors,namely N,N'-disecondary butyl-pphenylenediamine, lecithin, andN,N'-disalicylidene-1,2- diaminopropane.

These compositions are also similarly effective when tested in anaviation grade gasoline as exemplified by a /130 grade aviation gasolinecontaining 4.6 m1. of tetraethyl lead.

The motor fuels employed in this invention comprise a mixture ofhydrocarbons boiling in the gasoline boiling range. For instance, thegasoline employed can be a straight-run gasoline or a gasoline obtainedfrom a conventional cracking process, or mixtures thereof. The gasolinecan also include components obtained from processes other than crackingsuch as alkylation, isomerization, hydrogenation, polymerization,hydrodesulfuriza- 75 tion, hydroforming, platforming or combinationsthereof,

35 as well as synthetic gasoline obtained from the Fischer- Tropsch andrelated processes.

Test ll SPARK PLUG FOULING A production model 1956 Oldsmoble Super 88engine is used accomplish the evaluation. The engine is connecteddirectly to a power absorption dynamometer through a conventionalmultiple disc coupling. The dynamometer and engine are fullyinstrumented to control operating conditions and to indicate data whichare recorded hourly throughout the test.

Preparation of the engine for the test includes a thorough cleaning,inspection and measurement of all components. The engine is assembledaccording to the manufacturers specifications. After subjecting theengine to an eight hour break-in a thirty-two hour oil consumption checkfollows. During this check a speed of 2000 rpm. and 50 B.H.P. ismaintained. At eight hour intervals the oil is drained and weighed.Having established oil consumption stability the cylinder compressionpressures are measured to indicate valve condition. The cylinder headsare removed and all combustion chamber deposits eliminated.

The cylinder heads are assembled to the engine and preselected testspark plugs are installed for the first time. The engine starts on testschedule with an electromechanical intermittent controller attached tothe throttle and dynamometer control which timed and actuated thethrottle opening and dynamometer resistance for engine speed and loadchange. These changes are 2000 rpm. at 37.5 B.H.P. for five minutes and450 rpm. at idle for one minute. Fifty of these cycles or hourscomprised one interval. At the completion of each interval a check ismade for misfiring at 2400 rpm. at full load. If no misfiring isobserved the test continued for another interval of five hours. In theevent of misfiring, it is determined whether one or more spark plugs arefailing. A criterion for test termination is three fouled plugs in threedifferent cylinders. If less than three plugs fouled simultaneously thefouled plug or plugs are replaced with a new plug and the test continueduntil a total of three plugs fouled in three different cylinders. Thereasons for replacing the fouled plugs with new plugs before continuingthe test were:

A. To prevent upsetting test conditions which would effect fouling inother cylinders.

B. To assure that misfiring is caused by the plug or plugs in question.

C. To confirm that some abnormal condition in the cylinder is notcausing unusually early fouling.

The foregoing procedure and conditions are observed for the first 139hours of each test phase. At the end of 139 hours the conditionsconducive to spark plug fouling are further enhanced. Consideration iscarefully given to future possibility of test duplication before makingany change. Beginning with the 140th hour of each test phase andcontinuing until phase termination the following changes are in effect:

(1) The air fuel ratio is decreased from 12.4:1 to 11.1:1.

(2) The speed and load cycling is discontinued and changed to a constantspeed of 2200 r.p.m. at 41.2 B.H.P.

(3) As a consequence of the above changes the fuel flow increases from27.0 lbs/hr. to 40.0 lbs/hr.

(4) Instead of checking the spark plugs at five hour intervals at fullload, an observation with the Du Mont Engine Analyzer is made each hourWithout changing the speed or load unless plug fouling is detected.

Throughout the entire test a careful check is kept on oil consumption.At each 20 hours, as the test progressed, the engine is shut down for acrankcase oil level check. At each 60 hours the oil changed.

The fuel treated with the additive for the second phase of the test wasblended as follows:

A 4000 gallon capacity storage tank is flushed with the base fuel. 1200gallons of base fuel are pumped into the tank. A circulating pump isplaced in operation with the intake at one end of the tank and thedelivery at the opposite end of the required amount of additive is mixedwith five gallons of the base gasoline. This mixture is slowly fed intothe delivery stream of the fuel from the circulating pump. The fuelblend is recirculated for sixteen hours before start of the test.

The spark plugs selected for the test are AC-43. This spark plug is onedegree colder in the heat range than the engine manufacturer recommendsfor this model. Twenty-four plugs are inspected and pre-tested under airpressure for firing for each test phase. From each batch of 24 plugseight are selected which were nearly uniform in resistance at maximumpressure. All electrode gaps are adjusted to- .040.

Max. brake horsepower, at 4400 rpm. 240.

Carburetor Rochester 4-barrel Front Rear A/F Barrel Barrel Ratio Jetsizes Jet sizes Standard Equipment 49 51 13.1 1 0-139 hours of test 5551 12. 4 l hours to termination of test 59 55 11.1 1

Equipment air cleaner used. The air-fuel ratio was determined by aCambridge Exhaust Gas Tester.

Dynamometer: Mid West eddy current water cooled HP. capacity. Torquereaction measured by a Fairbanks Morse beam scale.

Instrumentation: The following temperatures were measured by means ofmercury thermometers:

Jacket coolant in Jacket coolant out Intake air at carburetor Motor oilin oil pan sump Wet bulb Dry bulb Exhaust back pressures and intakemanifold vacuum are measured by means of mercury manometers. Barometricpressures are observed on a conventional mercury barometer and wascorrected for temperature. Engine oil pressures are measured by astandard Bourdontype gage.

The rate of fuel consumption is determined on a weight basis using a tipbalance. A flowmeter in the supply line provides a check upon enginefuel consumption determined by weighing.

Engine speed is determined by an electronic counter.

Spark plug performance characteristics are observed by means of amultiple trace oscilloscope.

Both incipient fouling and 100% fouling of each spark plug is recordedin hours.

The base fuel used for the test operations is described as follows:CompositionMixture of straight run and catalytically cracked gasolines:

Gravity, API 58.8 Bromine number 53 Doctor Negative Sulfur, percent wt.0.017 Corrosion, Cu. strip, 3 hrs. at 122 F. None Gum, A.S.T.M., mg. 2.8

Oxidation stability, A.S.T.M., minutes 600 Octane number:

Fuels containing the compositions of this invention in weight percent of0.001 to 0.5% according to this test are superior to corresponding fuelscontaining no additive.

Since spark plug fouling is a function of the lead content of thegasoline, the optimum amount will vary with such content. Althoughweight ratios of 0.001-2% or more can be employed in gasolinescontainsabout 3 cc. of tetraethylene lead or its equivalent/gallon of gasoline,generally 0.0011% is usually sufficient for antifouling purposes.However, it should be understood that the optimum amount or the weightbases for one particular compound may not be the optimum amount foranother compound. One reason for this is that the efiect-iveness of thecompounds vary from one compound to another. Another reason is thevariance of molecular weights so that one compound may be twice themolecular weight of another on weight basis. However, by properadjustment of concentrations, anti-fouling can be effected. Theseprinciples also apply to the other ratios herein stated.

Test III These compounds in the above table are also tested in a 100hour full scale reciprocity engine test employing Military SpecificationMILG5572A grade 115/ 145 fuel in a Wright R3350-30W compound engineoperated according to the following cycle:

Time per cycle (min) Idle 10 Take-off power and speed 5 Normal ratedpower and speed 30 Cruise 90 normal rated power and 93% normal rated 30Cruise 90 Total 255 Test IV The compounds in the above tables are alsotested in a hour full scale gas turbine engine test in a Pratt & WhitneyJ57-P29 gas turbine engine employing Specification MILJ-5624D Grade JP-4fuel. The engine is operated for 100 hours and cycled in accordance withthe Specification MIL-E-5009 Model qualification test. After 100 hoursof operation, the engine combustion components and turbine sections aredisassembled and inspected for deposits and deleterious effects.

Fuels containing the compositions of this invention in weight ratios of0.001 to 0.5 by weight according to this test are superior tocorresponding fuels containing no additive.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications may be resortedto without departing from the spirit and scope thereof. For example, theinvention includes the reaction product of other amines besides thosespecifically stated above, for example heterocyclie amines, such asaminooxazolenes, for example wherein R is a hydrocarbon, and homologousthereof,

wherein R and R are for example alkyl or hydrogen,

I] ]TH NH2-(CH2)ioC-NH2, etc.

In addition, the invention includes various fuels such as all grades ofgasolines which may contain a wide variety of additives such asanti-oxidants, organolead stabilizers, organic dyes, solubilizers, etc.,as well as the halide scavengers generally employed such as ethylenedibromide and/or ethylene dichloride and other scavengers for examplethose disclosed in the patents listed above relating to suchcompositions. Such variations and modifications are considered to bewithin the purview and scope of the appended claims.

Having thus described my invention, what I claim as new and desire toobtain by Letters Patent is:

1. A process of preventing, inhibiting and modifying the formation ofdeposits in internal combustion and jet engines employing asubstantially hydrocarbon fuel which comprises burning in such engines afuel consisting of a liquid hydrocarbon having a boiling point up toabout 500 F. and a minor amount in the range of approximately 0.001 to 2weight percent of said fuel, suflicient to prevent, inhibit and modifysuch deposits, of a reaction product of (1) a member selected from thegroup consisting of an alkenyl succinic acid and the anhydride thereof,having 3-32 carbon atoms on the alkenyl group and (2) an amine having atleast one carbon atom, the sum of the carbons on said acid and saidanhydride plus the carbons on said amine totalling from approximately 10to approximately 82 carbon atoms, said reaction product being soluble insaid liquid hydrocarbon and being composed of only carbon, hydrogen,nitrogen and oxygen.

jet engines employing asubstantially hydrocarbon fuel which comprisesburning in such engines a fuel consisting of a liquid hydrocarbon havinga boiling point up to about 500 F. and a minor amount in the range ofapproximately 0.001 to 2 weight percent of said fuel, sufficient toprevent, inhibit and modify such deposits, of a reaction product of (1)two moles of a member selected for the group consisting of an alkenylsuccinic' acid and the anhydride thereof, having three thirty-two carbonatoms on the alkenyl group and (2) one mole of an aminoalkanol having atleast three carbon atoms, the sum of the carbons on said acid and saidanhydride plus the carbons on said amine totaling from axxporixately toapproximately 82 carbon atoms, said reaction product being soluble insaid liquid hydrocarbon and being composed of only carbon, hydrogen,nitroegn and oxygen.

3. The process of claim 1 wherein the hydrocarbon fuel is gasoline.

4. The process of claim 3 where the amine is a monoamine.

5. The process of claim 3 where the amine is a polyamine.

6. The process of claim 3 where the amine is a hydroxyl monoamine.

7. The process of claim 3 where the amine is a hydroxyl polyamine.

8. The process of claim 1 wherein the hydrocarbon fuel is a jet fuel.

9. The process of claim 8 where the amine is a monoamine.

10. The process of claim 8 where the amine is a polyamine.

1-1. The process of claim 8 where the amine is a hydroxyl monamine.

12. The process of claim 8 where the amine is a hydroxyl polyamine.

13. The process of claim 2 wherein the substantially hydrocarbon fuel isgasoline.

14. The process of claim 13 wherein the alkenyl group has 8-18 carbonatoms and the aminoalkanol has 38 carbon atoms.

15. The process of claim 13 wherein the alkenyl group has 8-18 carbonatoms and the aminoalkanol is 16. The process of claim 2 wherein thesubstantially hydrocarbon fuel is a jet fuel.

17. The process of claim 16 wherein the alkenyl group has 818 carbonatoms and the aminoalkanol has 38 carbon atoms.

18. The process of claim 16 wherein the alkenyl group has 8-18 carbonatoms and the aminoalkanol is 19. The process of claim 15 wherein thealkenyl group is tetrapropenyl.

2 0. The process of claim 18 wherein the alkenyl group is tetrapropenyl.

References Cited in the file of this patent UNITED STATES PATENTS2,386,445 De Groote Oct. 9, 1945 2,450,221 Ashburn et a1 Sept. 28, 19482,568,746 Kirkpatrick Sept. 25, 1951 2,715,108 Francis Aug. 9, 19552,733,235 Cross et al. Jan. 31, 1956

1. IN A PROCESS OF PREVENTING, INHIBITING AND MODIFYING THE FORMATION OFDEPOSITS IN INTERNAL COMBUSTION AND JET ENGINES EMPLOYING ASUBSTANTIALLY HYDROCARBON FUEL WHICH COMPRISES BURNING IN SUCH ENGINES AFUEL CONSISTING OF A LIQUID HYDROCARBON HAVING A BOILING POINT UP TOABOUT 500*F. AND A MINOR AMOUNT IN THE RANGE OF APPROXIMATELY 0.001 TO 2WEIGHT PERCENT OF SAID FUEL, SUFFICIENT TO PREVENT, INHIBIT AND MODIFYSUCH DEPOSITS, OF A REACTION PRODUCT OF (1) A MEMBER SELECTED FROM THEGROUP CONSISTING OF AN ALKENYL SUCCINIC ACID AND THE ANHYDRIDE THEREOF,HAVING 3-32 CARBON ATOMS ON THE ALKENYL GROUP AND (2) AN AMINE HAVING ATLEAST ONE CARBON ATOM, THE SUM OF THE CARBONS ON SAID ACID AND SAIDANHYDRIDE PLUS THE CARBONS ON SAID AMINE TOTALLING FROM APPROXIMATELY 10TO APPROXIMATELY 82 CARBON ATOMS, SAID REACTION PRODUCT BEING SOLUBLE INSAID LIQUID HYDROCARBON AND BEING COMPOSED OF ONLY CARBON, HYDROGEN,NITROGEN AND OXYGEN.